Zeitschriftenaufsätze

The electrodeposition of aluminum-nickel coatings was performed by pulsed direct current in the ionic liquid (IL) 1.5:1 AlCl3:EMIm]Cl containing nickel nanoparticles (Ni NPs), for reactive dispersion coating application. Several electrochemical and characterization techniques were used to shed more light on the mechanism of Ni particle incorporation into the Al matrix. Thus, particle incorporation at the early stage of the deposition would mainly take place via particle adsorption at the substrate. However, as the thickness of the coating increases, it seems that the main mechanism for particle incorporation is via the reduction of ions adsorbed at the particles surface. Although a considerable high incorporation of Ni NPs has been achieved from the IL containing the highest concentration of Ni NPs (i.e. ∼33 wt% from a 20 g/L of Ni NPs bath), a high concentration of NPs in the IL resulted having a negative effect in terms of quality of the coatings, due to solidification of the electrolyte in a poorly conductive compound. Moreover, almost equivalent amounts of Ni and Al (Ni ∼45 wt.%and Al ∼44 wt.%) have been detected in some areas of the coatings. Such a layer composition would be desired for the targeted application.

In metal-air batteries, the integrated solid-state cathode is considered a promising design because it can solve the problem of high interfacial resistance of conventional solid-state cathodes. However, solid discharge products cannot be efficiently decomposed in an integrated solid-state cathode, resulting in batteries that are unable to operate for long periods of time. Herein, an integrated solid-state cathode (Gel-Tempo cathode) of sodium-air batteries (SABs) capable of promoting efficient decomposition of discharge product Na2O2 is designed. The Gel-Tempo cathode is synthesized by cationic-π interaction of redox mediator 2,2,6,6-tetramethyl-1-piperidinyloxy (Tempo) and ionic liquid with carbon nanotubes. The Gel-Tempo cathode serves multiple functions as a redox mediator, flame retardancy, and high stability to air. In quasi-solid-state SABs, the Gel-Tempo cathode reduces overpotential to 1.15 V and improves coulomb efficiency to 84.5% (at a limited discharge capacity of 3000 mAh g−1) compared to gel cathodes. Experiments and density functional theory calculations indicate that Tempo significantly reduces the Gibbs free energy in the decomposition reaction of Na2O2, and high Tempo content is more conducive to enhancing the decomposition kinetics of Na2O2 and hence resulting in an ultra-long cycle life (1746 h). This work is crucial to promote practical applications of SABs, providing guidelines for functionalization design of integrated solid-state cathodes for metal-air batteries.

In reservoir rocks, the term “ageing” refers to extended exposition to crude oil; a typically water-wet sandstone will then gradually become oil-wet as a consequence of the deposition of insoluble fractions of oil onto the surface grains. Rocks have been aged artificially by subjecting them to a bitumen solution at elevated temperature in order to achieve comparable surface properties for three different types of rock: Bentheimer, Berea Buff and Liège Chalk. Using saturated and aromatic model compounds as proxies for crude oil, the nuclear magnetic resonance (NMR) relaxation dispersion in native and aged rocks was compared and correlated to the properties of paramagnetic impurities in these rock types. Perfluorated liquids were found to follow the same trend as deuterated and naturally occurring oil components, suggesting they can be used as suitable tracers for wettability studies since the 19F nucleus is absent in natural sources. By combining electron paramagnetic resonance (EPR) and dynamic nuclear polarization (DNP) it becomes possible to identify and quantify the origin of the dominating relaxation processes between native and aged rocks, providing an alternative approach to assess wettability in natural rocks.

Identifying an effective electrolyte is a primary challenge for hybrid ion capacitors, due to the intricacy of dual-ion storage. Here, this study demonstrates that the electrochemical behavior of graphite oxide in ether-solvent electrolyte outperforms those in ester-solvent electrolytes for the cathode of potassium-ion hybrid capacitor. The experimental and theoretical assessments verify that the anion and cation are isolated effectively in dimethyl ether, endowing a weaker interaction between cations and anions compared to that of ester-solvent electrolytes, which facilitates the dual-ion diffusion and thus enhances the electrochemical performance. This result provides a rational strategy to realize high-rate cations and anions storage on the carbon cathode. Furthermore, a new low-cost and high-performance capacitor prototype, modified graphite oxide (MGO) cathode versus pristine graphite (PG) in ether-solvent electrolyte (MGOǁDMEǁPG), is proposed. It exhibits a high energy density of 150 Wh kg^−1cathode at a high power density of 21443 W kg^−1cathode (calculation based on total mass: 60 Wh kg^−1 at 8577 W kg^−1).

In the current work, the rational synthesis of trinuclear copper complexes, incorporating acute bite angle POP- and PSP-type ligands, is reported. The in situ formation of POP (Ph2P–O–PPh2) or PSP (Ph2P–S–PPh2) ligands in the presence of a copper(I) precursor gave access to various trinuclear copper complexes of the form [Cu3(μ3-Hal)2(μ-PXP)3]PF6 [X = O; Hal = Cl (1), Br (2), I (3) and X = S; Hal = Cl (5), Br (6), I (7)]. Related iodide-containing complexes and clusters, such as [Cu4(μ3-I)4(Ph2PI)4] (4) and [Cu3(μ3-I)2(μ-I)(μ-PSP)2] (8), could also be obtained via the variation of the reaction stoichiometry. The investigation of the photo-optical properties by photo-luminescence spectroscopy has demonstrated that the phosphorescence in the visible region can be switched off through the mere change of the heteroatom in the ligand backbone (POP vs PSP ligand scaffold). Theoretical studies have been conducted to complement the experimental photo-optical data with detailed insights into the occurring electronic transitions. Consequently, this systematic study paves the way for tuning the photo-optical properties of transition metal complexes in a more rational way.